Note: Descriptions are shown in the official language in which they were submitted.
CA 0220~117 1996-0~-12
FM/6-20199/A
1~ T~ L~
-
Thermal metathesis PolYmerization Process and a Polvmerizable co",posilion
The present invention relates to a prucess for the thermal polymerization of strained
cycloolefins; a thermally polymerizable composition of such a cycloolefin and a one-
component catalyst for thermally induced metathesis polymerization; and carrier materials
coated with the thermally polymerizable or the cl ossli"ked polymers.
Demonceau et al. [Demonceau, A., Noels, A.F., Saive, E., Hubert, A.J., J. Mol. Catal.
76:123-132 (1992)l describes [(C6H5)3P]3RuCI2, (p-cumene)RuCI2P(C6H")3 and
[(C6H5)3P]3RuHCI as thermal catalysts for ring-opening metathesis polymerization of
norbomene, a fused polycycloolefin. Because the activity is too low, these catalysts have not
found acceptance in industrial preparaLion. It has therefore been suggested that the activity
be increased by the addition of diazo esters. It is also mentioned that only (p-cumene)RuCI2P(C6H")3 is cap,, ~le of polymerizing norbornene in a relatively short time at
60C. Cyclooctene is also mentioned as a further monomer.
WO 93/13171 des.;,il.es air- and water-stable one-component and two-component catalysts
based on molybdenum compounds and tungsten compounds containing carbonyl groups
and ruthenium compounds and osmium compounds with at least one polyene ligand for the
thermal metathesis polymerization and a photoactivated metathesis polymerization of
strained cycloolefins, in particular norbomene and norbornene derivatives. No other
polycyclical - above all non-fused polycyclical - cycloolefins are mentioned. The one-
component catalysts of the ruthenium compounds used, that is to say [Ru(cumene)CI2]2 and
[(C6H6)Ru(CH3CN)2Cl]'PF6-, can indeed be activated by UV i"~didlion; however, the storage
stability of the cor"posilions with norbomene is completely inadequate. These catalysts are
c~p7~'e of replacing the known two-component catalysts only inadequately.
It has now been found, s~ .ri~i"yly, that divalent-cationic ruthenium and osmium complexes
are highly active one-component catalysts for thermally induced metathesis polymerization if
they contain at least one phosphine group with bulky substituents bound to the metal atom. It
has furthermore been found that the compositions are stable to air and moisture and can be
processed without safety prec~utions. The polymerizable compositions comprising
ruthenium and osmium complexes are moreover sufficiently stable, so that they do not
polymerize before the desired type of ~rocessing.
CA 0220~117 1996-0~-12
-- 2 --
The invention relates to a composition of (a) at least one strained cycloolefin and (b) a
catalytic quantity of at least one divalent-cationic compound of ruthenium or osmium,
wherein the ruthenium or osmium compound contains a metal atom to which are bound 1 to
3 tertiary phosphine ligands with, in the case of the ruthenium compounds, sterically exacting
substituents, optionally non-photolabile neutral ligands and anions for charge balancing, with
the proviso that in ruthenium (trisphenylphosphine)dil ,-' des or hydride-halides the phenyl
groups are sllhstitlltpd by C,-C,8alkyl, C,-C,8haloalkyl or C,-C,8alkoxy.
The cyclical olefins can be monocyclical or polycyclical condensed or bridged ring systems,
having for example from two to four rings, which are unsl Ihstihlted or suhstitut~d and can
contain heterc,dlo"1s, for example 0, S, N or Si in one or more rings and/or can contain
condensed aromatic or heteroar~",alic rings, for example o-phenylene, o-naphthylene, o-
pyridinylene or o-pyrimidinylene. The individual cyclical rings can contain 3 to 16, p,~fer~bly
3 to 12 and, particularly prererably, 3 to 8 ring members. The cyclical olefins can include
further nonaromatic double bonds, depending on the ring size preferably 2 to 4 such
additional double bonds. The ring s~ ~hstituents are those which are inert, in other words
which do not adversely affect the chemical stability of the ruthenium compounds and
osmium compounds. The cycloolefins are strained rings or ring systems.
If the cyclical olefins contain more than one double bond, for example 2 to 4 double bonds,
crosslinked polymers can also form, depending on the reaction condilions, the monomer
chosen and the amount of catalyst.
In a p,t:~r,ed embodiment of the process according to the invention, the cycloolefins
cor, espond to the formula I
CH CQ
\ / (1),
Q1
in which
Q, is a radical having at least one carbon atom which, together with the -CH=CQ2 group,
forms an at least 3-membered alicyclical ring which optionally cor,lai"s one or more
heteroatoms chosen from the group consiili-,g of silicon, phosphorus, oxygen
nitrogen and sulfur; and which is unsl ~hstitnted or sl Ihstitllted by halogen, =0, -CN,
CA 0220~117 1996-0~-12
-NO2, R1R2R3Si-(O)U-,-COoM~-so3M~-po3M~-coo(M1)w-so3(M~ 2~-po3(Ml)1/2
C1-C20-alkyl, C,-C20hydroxyalkyl, C,-C20haloalkyl, C,-C6cyanoalkyl, C3-C8cycloalkyl,
C6-C,6aryl, CrC,6aralkyl, C3-C6heterocycloalkyl, C3-C,6heteroaryl, C4-C,6heteroaralkyl
or R4-X-; or in which two adjacent C atoms are substituted by -CO-O-CO- or-CO-
NRs-CO-; or in which an alicyclical, aromatic or heteroaromatic ring which is
unsl ~hstituted or substituted by halogen, -CN, -NO2, R6R7R8Si-(O)U-, -COOM, -SO3M,
-PO3M, -COO(M,)"2, -SO3(M,)"2, -PO3(M,)"2, C,-C20alkyl, C,-C20haloalkyl,
C,-C20hydroxyalkyl, C1-C6cyanoalkyl, C3-C8cycloalkyl, C6-C16aryl, C7 C16aralkyl,C3-C6heterocycloalkyl, C3-C16heteroaryl, C4-C16h~:teroa,all;yl or R13-X,- is optionally
fused onto adjacent carbon atoms of the alicyclical ring;
X and X, independently of one another are -O-, -S-, -CO-, -SO-, -SO2-, -O-C(O)-, -C(O)-Q-,
-C(O)-NRs-, -NR,0-C(O)-, -SO2-O- or-O-S02-;
R" R2 and R3 independently of one another are C,-Cl2alkyl, C,-C,2perfluoroalkyl, phenyl or
benzyl;
R4 and R,3 independently are C,-C20alkyl, C,-C20haloalkyl, C,-C20hydroxyalkyl,
C3-C8cycloalkyl, C6-C,6aryl or CrC,6aralkyl;
R5 and R~o independently of one another are hydrogen, C1-C12alkyl, phenyl or benzyl, where
the alkyl groups in turn are unsubstituted or silhstitllted by C1-C12alkoxy or
C3-C8cycloalkyl;
R6, R~ and R8 independently of one another are C,-C,2alkyl, C,-C,2per~uoroalkyl, phenyl or
benzyl;
M is an alkali metal and M, is an alkaline earth metal; and
uisOor1;
where the alicyclical ring formed with Q1 optionally contains further nonaromatic double
bonds;
Q2 is hydrogen, C,-C20alkyl, C,-C20haloalkyl, C,-C12alkoxy, halogen, -CN or R11-X2-;
R11 is C,-C20alkyl, C,-C20haloalkyl, C,-C20hydroxyalkyl, C3-C8cycloalkyl, C6-C16aryl or
CrC16aralkyl;
X2 is -C(O)-O- or -C(O)-NR12-;
R12 is hydrogen, C1-C12alkyl, phenyl or benzyl;
where the abovementioned cycloalkyl, heterocycloalkyl, aryl, heteroaryl, aralkyl and
heteroaralkyl groups are unsubstituted or sl Ihsfftl Ited by C1-C12alkyl, C1-C12alkoxy, -NO2, -CN
or halogen, and where the heteroatoms of the abovementioned heterocycloalkyl, heteroaryl
and heteroaralkyl groups are chosen from the group consi~li"g of -O-, -S-, -NRg- and -N=;
and
R8 is hydrogen, C1-C,2alkyl, phenyl or benzyl.
CA 0220~117 1996-0~-12
Fused-on alicyclical rings preferably contain 3 to 8, particularly preferably 4 to 7, and
especially preferably 5 or 6 ring C atoms.
If an asymmetric center is present in the compounds of the formula 1, the compounds can
occur in optically isomeric forms as a result. Some compounds of the formula I can occur in
tautomeric forms (for example keto-enol tautomerism). If an aliphatic C=C double bond is
present, geometric isomerism (E form or Z form) can also occur. Exo-endo configurations
are furthermore also possible. Formula I thus includes all the possiL)le stereoisomers which
are present in the form of enantiomers, tautomers, diastereomers, E/Z isomers or mixtures
thereof.
In the definitions of the s~hstitllents, the alkyl, alkenyl and alkynyl groups can be straight-
chain or branched. The same also applies to the alkyl or each alkyl moiety of alkoxy,
alkylthio, alkoxycarbonyl and further alkyl-conLd;"i"g groups. These alkyl groups preferably
contain 1 to 12, more preferably 1 to 8, and particularly preferably 1 to 4 C atoms. These
alkenyl and alkynyl groups pr~::r~rdbly contain 2 to 12, more preferably 2 to 8, and particularly
preferably 2 to 4 C atoms.
Alkyl includes, for example, methyl, ethyl, isopropyl, n-propyl, n-butyl, iso-butyl, sec-butyl,
tert-butyl and the various isomeric pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl,
tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl
radicals.
Hydroxyalkyl includes, for example, hydroxymethyl, hydroxyethyl, 1-hydroxyisopropyl, 1-
hydroxy-n-propyl, 2-hydroxy-n-butyl, 1-hydroxy-iso-butyl, 1-hydroxy-sec-butyl, 1-hydroxy-
tert-butyl and the various isomeric pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl,
tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl
radicals.
Haloalkyl includes, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl,
dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, 2,2,2-
trichloroethyl and halogenated, in particular fluorinated or chlorinated, alkanes, such as, for
example, the isopropyl, n-propyl, n-butyl, iso-butyl, sec-butyl and tert-butyl and the various
isomeric pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl,
pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl and eicosyl radicals.
~ CA 0220~117 1996-0~-12 ~
.,
-5-
Alkenyl includes, for example, propenyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl,
n-penta-2,4-dienyl, 3-methyl-but-2-enyl, n-oct-2-enyl, n-dodec-2-enyl, iso-dodecenyl,
n-octadec-2-enyl and n-octadec-4-enyl.
Cycloalkyl is preferably Cs-C8cycloalkyl, in particular Cs-or C6cycloalkyl. Some examples are
cyclopropyl, dimethylcycloprupyl, cyclobutyl, cyclopentyl, methylcyclopentyl, cyclohexyl,
cycloheptyl and cyclooctyl.
Cyanoalkyl includes, for example, cyanomethyl (methylnitrile [sic]), cyanoethyl (ethylnitrile
[sic]), 1-cyanoisopropyl, 1-cyano-n-propyl, 2-cyano-n-butyl, 1-cyano-iso-butyl, 1-cyano-sec-
butyl, 1-cyano-tert-butyl and the various isomeric cyanopentyl and -hexyl radicals.
Aralkyl preferably contains 7 to 12 C atoms, and particularly preferably 7 to 19 C atoms. It
can be, for example, benzyl, phenethyl, 3-phenylpropyl, a-methylbenzyl, phenbutyl or
a,a-dimethylbenzyl.
Aryl preferably contains 6 to 10 C atoms. It can be, for example, phenyl, penlali", indene,
naphthalene, azulene or anthracene.
Heteroaryl preferably cor,Ldi"s 4 or 5 C atoms and one or two heteroatoms from the group
consisting of 0, S and N. It can be, for example, pyrrole, furan, thiophene, oxazole, thiazole,
pyridine, pyrazine, pyrimidine, pyridazine, indole, purine or quinoline.
Heterocycloalkyl pr~r~rdbly contains 4 or 5 C atoms and one or two heteroatoms from the
group consisli"g of 0, S and N. It can be, for example, oxirane, azirine, 1,2-oxathiolane,
pyrazoline, pyrrolidine, piperidine, piperazine, morpholine, tetrahydrofuran or
tetrahydrothiophene.
Alkoxy is, for example, methoxy, ethoxy, propyloxy, i-propyloxy, n-butyloxy, i-butyloxy, sec-
butyloxy and t-butyloxy.
Alkali metal in the context of the present invention is to be understood as meaning lithium,
sodium, potassium, rubidium and cesium, in particular lithium, sodium and poLassium.
CA 0220~117 1996-0~-12
Alkaline earth metal in the context of the present invention is to be understood as meaning
beryllium, magnesium, calcium, strontium and barium, in particular magnesium and calcium.
In the above deri"ilions, halogen is to be understood as meaning fluorine, chlorine, bromine
and iodine, preferably fluorine, chlorine and bromine.
Compounds of the formula I which are particularly s~ ~it~'e for the process according to the
invention are those in which Q2 is hydrogen.
Compounds of the formula I which are furthermore preferred for the polymerization are those
in which the alicyclical ring which Q, forrns together with the -CH=CQ2- group has 3 to 16,
more preferably 3 to 12, and particularly preferably 3 to 8 ring atoms, where the ring system
can be monocyclical, bicyclical, tricyclical or tetracyclical.
The process according to the invention can be carried out particularly advantageously with
those compounds of the formula I in which
Q, is a radical with at least one carbon atom which, together with the -CH=CQ2- group,
forms a 3- to 20-membered alicyclical ring which optionally contains one or moreheteroatoms chosen from the group cons;sling of silicon, oxygen, nitrogen and sulfur;
and which is unsl ~hstituted or svhstituted by halogen, =O, -CN, -NO2, R1R2R3si-(o)
-COOM, -SO3M, -PO3M, -COO(M,)"2, -SO3(M,)"2, -PO3(M,)"2, C,-C,2alkyl,
C,-C,2haloalkyl, C,-C,2hydroxyalkyl, C,-C4cyanoalkyl, C3-C6cycloalkyl, C6-C,2aryl,
CrC,2aralkyl, C3-C6heterocycloalkyl, C3-C,2heteroaryl, C4-C,2heteroaralkyl or R4-X-; or
in which two adjacent C atoms in this radical Q,are 5llhstitllted by -CO-O-CO- or
-CO-NRs-CO-; or in which an alicyclical, aromatic or heteroaromatic ring which is
unsl ~hstihlted or sl ~bstihlted by halogen, -CN, -NO2, R6R7R8Si-, -COOM, -SO3M,-PO3M, -COO(M,)1,2, -SO3(M,)"2, -PO3(M,)"2, C,-C,2alkyl, C,-C,2haloalkyl,
C,-C,2hydroxyalkyl, C,-C4cyanoalkyl, C3-C6cycloalkyl, C6-C,2aryl, C7-C,2aralkyl,C3-C6heterocycloalkyl, C3-C,2heteroaryl, C4-C,2heteroaralkyl or R,3-X,- is optionally
fused onto adjacent carbon atoms;
X and X, independently of one another are -O-, -S-, -CO-, -SO-, -SO2-, -O-C(O)-, -C(O)-O-,
-C(O)-NRs-, -NR,0-C(O)-, -SO2-O- or-O-SO2-;
R" R2 and R3 independently of one another are C,-C6alkyl, C,-C6perfluoroalkyl, phenyl or
benzyl;
M is an alkali metal and M, is an alkaline earth metal;
CA 0220~117 1996-0~-12
--7 --
R4 and R,3 independently of one another are C,-C,2alkyl, C,-C12haloalkyl, C,-C,2hydroxyalkyl,
C3-C8cycloalkyl, C6-C,2aryl or C7-C,2aralkyl;
R5 and R,o independently of one another are hydrogen, C1-C6alkyl, phenyl or benzyl, where
the alkyl groups in turn are unsubstituted or substituted by C~-C6alkoxy or
C3-C6cycloalkyl;
R6, R7 and R8 independently of one another are C,-C6alkyl, C,-C6perfluoroalkyl, phenyl or
benzyl;
uisOor1;
where the alicyclical ring formed with Q, optionally contains further nonaromatic double
bonds;
Q2 is hydrogen, C,-C,2alkyl, C,-C,2haloalkyl, C,-C6alkoxy, halogen, -CN or R"-X2-;
R" is C,-C,2alkyl, C,-C,2haloalkyl, C,-C,2hyclroxyalkyl, C3-C6cycloalkyl, C6-C,2aryl or
C7-C,2aralkyl;
X2 is -C(O)-O- or-C(O)-NR,2; and
R-2 is hydrogen, C,-C6alkyl, phenyl or benzyl;
where the cycloalkyl, heterocycloalkyl, aryl, heteroaryl, aralkyl and heteroaralkyl groups are
unsubstituted or substituted by C,-C6alkyl, C,-C6alkoxy, -NO2, -CN or halogen, and
where the helerudLoms of the heterocycloalkyl, heteroaryl and heteroaralkyl groups
are chosen from the group cons,~ ,g of -O-, -S-, -NRg- and -N=; and
R~ is hydrogen, C,-C6alkyl, phenyl or benzyl.
Preferred compounds of the formula I from this group are those in whichQ, is a radical with at least one carbon atom which, together with the -CH=CQ2- group,
forms a 3- to 1 O-membered alicyclical ring which opLiondlly contains a heteroatom
chosen from the group consi~li"g of silicon, oxygen, nitrogen and sulfur and is
unsllhstituted orsllhstituted by halogen, -CN, -NO2, R,R2R3Si-, -COOM, -SO3M,
-PO3M, -COO(M,)"2, -SO3(M,)"2, -PO3(M,)"2, C,-C6alkyl, C,-C6haloalkyl,
C,-C6hydroxyalkyl, C,-C4cyanoalkyl, C3-C6cycloalkyl, phenyl, benzyl or R4-X-; or in
which an alicyclical, aromatic or heteroaromatic ring which is unsubstituted or
sllhstituted by halogen, -CN, -NO2, R6R~R8Si-, -COOM, -S03M, -PO3M, -COO(M,)"2, -
SO3(M,)"2, -PO3(M,)"2, C,-C6alkyl, C,-C6haloalkyl, C,-C6hydroxyalkyl,
C,-C4cyanoalkyl, C3-C6cycloalkyl, phenyl, benzyl or R,3-X,- is optionally fused onto
adjacent carbon atoms;
R" R2 and R3 independently of one another are C,-C4alkyl, C,-C4perfluoroalkyl, phenyl or
benzyl;
M is an alkali metal and M, is an alkaline earth metal;
CA 0220~117 1996-0~-12
-- 8 --
R4 and R,3 independently of one another are C1-C6alkyl, C,-C6haloalkyl, C1-C6hydroxyalkyl or
C3-C6cycloalkyl;
X and X, independently of one another are -O-, -S-, -CO-, -SO- or -SO2-;
R6, R7 and R8 independently of one another are C,-C4alkyl, C1-C4perfluoroalkyl, phenyl or
benzyl;
and Q2 is hydrogen.
The process according to the invention is particularly suitable for polymerization of
norbornene and norbornene derivatives. Particularly preferred compounds from these
norbornene derivatives are those which correspond either to the formula ll
(Il).
~3
~R14
in which
X3 is -CHR,6-, oxygen or sulfur;
R14 and R,5 independently of one another are hydrogen, -CN, trifluoromethyl, (CH3)3Si-O-,
(CH3)3Si- or-COOR17; and
R.6 and R,7 independently of one another are hydrogen, C,-C,2-alkyl, phenyl or benzyl;
or to the formula lll
~ (111)
R.8
in which
X4 is -CHR19-, oxygen or sulfur;
R,9 is hydrogen, C,-C,2alkyl, phenyl or benzyl; and
R.8 is hydrogen, C,-C6alkyl or halogen;
or to the formula IV
~ CA 0220~117 1996-0~-12 ~
_ g _
(IV),
~ R20
in which
Xs is -CHR22-, oxygen or sulfur;
R22 is hydrogen, C1-C,2alkyl, phenyl or benzyl;
R20 and R2, independently of one another are hydrogen, CN, trifluoromethyl, (CH3)3Si-O-,
(CH3)3Si- or-COOR23; and
R23 is hydrogen, C,-C,2alkyl, phenyl or benzyl;
or to the formula V
X6~Y ~,
(~0
in which
)(6 is -CHR24-, oxygen or sulfur;
R24 is hydrogen, C,-C12alkyl, phenyl or benzyl;
Y'
Is oxygen or N--R2s . and
R2s is hydrogen, methyl, ethyl or phenyl.
The following compounds of the formula I are particularly s~ le for the polymerization
process according to the invention, bi- and polycyclical systems being ~ccessihle by Diels-
Alder reactions:
CA 62265117 1996-65-12
-10-
~\ COOH ~\ _COOCH,
(1), ~ (2), ~y (3),
COOH COOCH3
COOCH2-Phenyl ~ COOCH2CH3
COOCH2-Phcnyl COOCH2CH3
O O
(CH2)3CH~ (6) ~ COO(CH2),CH3 (7
COO(CH2)3CH, COO(CH2)sCHJ
o o
(CH2)'CH3 (8) ~ COO(CH2)"CH3
COO(CH2)~CH3 COO(CH2)"CH3
~CN (10), ~CH2O(CH2)socH3 (11),
(c~Hs)2 (12) ~ Si(CH3)3 (1 3),
P(C3Hs)2
CA 1l22osll7 1996-115-12
~CH2NHCH3 (14)/7~ // (15),
CH2NHCH3 ~C
~ (16), ~ (17),
o
~/c ~
~3 (20),~-- (21)~
(22), ~ (23),
CA 1l22osll7 1 96-llS-12
(24), ~(25),
CH, o
~oc~, (26), 9 (27), ~) (28),
H,CO
@J (29), ~¦ (30), 13 (31),
~> (32), ~ (33)~ ~ (34),
~3X~3 (35) ~CH3 (36),
H3CO
l-l,CO~ ~ F,C~ ;~ (38),
CA 0220~ll7 l996-0~-l2
- 13-
~3 (39), ~ ~ (40).
~3(41)' ~1 (42),
~ (43) and G ~ (44)
In a preferred embodiment, the cycloolefins contain only carbon and hydrogen atoms, and
are preferably 5- or 6-membered rings or ring systems with one to three 5- or 6-membered
rings, for example norbornene, alkylated norbornenes and dicyclopentadiene.
The ruthenium and osmium compounds preferably contain 2 or 3 tertiary phosphine groups.
Phosphine groups in the context of the invention are understood as meaning tertiary
phosphines. The number of additional non-photolabile neutral ligands depends on the one
hand on the number of phosphine ligands and on the other hand on the valency of the
neutral ligands. Monovalent neutral ligands are preferred.
In a preferred embodiment, the divalent-cationic ruthenium and osmium compounds to be
used accordi"g to the invention contain 3 phosphine groups and 2 monovalent anions for
charge balancing; or 3 phosphine groups, two monovalent or one divalent non-photolabile
neutral ligands, and two monovalent anions for charge balancing; or 2 phosphi"e groups,
one monoanionic, additionally monovalent non-photolabile neutral ligands, and one
monovalent anion for charge balancing.
~ CA 0220~117 1996-0~-12 ~
-
- 14-
Non-photolabile ligand (also called highly coordinating ligand) in the context of the present
invention means that the ligand does not dissociate, or dissociates to only an insignificant
extent, from the catalyst on i" ~dialion of the catalyst in the visible or near ultraviolet range of
the spectrum.
The monoanionic, additionally monovalent non-photolabile neutral ligands are preft:r~bly
cyclopenla.lianyl or indenyl, which are uns~hstituted or s~ ~hstituted by 1 to 5 C,-C4alkyl, in
particular methyl, or -Si(C,-C4alkyl), in particular -Si(CH3)3.
The non-photolabile ligands can be, for example, solvating inorganic and organiccompounds which contain the heteroator"s O, S or N and are often also used as solvents.
Examples of such compounds are H2O, H2S, NH3; optionally halogenated, in particular
fluorinated or chlorinated, aliphatic or cyclo31iphatic alcohols or me,~aptans having 1 to 18,
preferably 1 to 12, and particularly preferably 1 to 6 C atoms, aror"~lic alcohols or thiols
having 6 to 18, preferably 6 to 12 C atoms, araliphatic alcohols or thiols having 7 to 18,
preferably 7 to 12 C atoms; open-chain or cyclical and ali~,halic, araliphatic or aromatic
ethers, thioethers, sulfoxides, sulfones, ketones, aldehydes, carboxylic acid esters, lactones,
optionally N-C,-C4mono- or-dialkylated carboxylic acid amides having 2 to 20, preferably 2
to 12, and in particular 2 to 6 C atoms, and optionally N-C,-C4alkylated lactams; open-chain
or cyclical and aliphatic, ara'i,.h~lic or aromatic primary, secondary and tertiary amines
having 1 to 20, preferably 1 to 12, and particularly preferably 1 to 6 C atoms.
Examples of such non-photolabile ligands are methanol, ethanol, n- and i-propanol, n-, i- and
t-butanol, 1,1,1-trifluoruell,anol, bistrifluorornell,ylmethanol, tristrifluoromethylmethanol,
pentanol, hexanol, methyl- or ethylmer-;apl~n, cyclopentanol, cyclohexanol,
cyclohexylmercaptan, phenol, methylphenol, fluorophenol, phenylmercaptan,
benzylmercaptan, benzyl alcohol, diethyl ether, dimethyl ether, diisopropyl ether, di-n- or di-t-
butyl ether, tetrahydrofuran, tetrahydropyran, dioxane, diethyl thioether, tetrahydlc,ll,iophene,
dimethyl sulfoxide, diethyl sulfoxide, tetra- and pentamethylene sulfoxide, dimethyl sulfone,
diethyl sulfone, tetra- and pentamethylene sulfone, acetone, methyl ethyl ketone, diethyl
ketone, phenyl methyl ketone, methyl isobutyl ketone, benzyl methyl ketone, acetaldehyde,
propion-'dehyde, trifluoro~Get.-'dehyde, benzaldehyde, ethyl acetate, butyrolactone,
dimethylformamide, dimethylacelar"ide, pyrrolidone and N-methylpy"o' done, indenyl,
cyclopenladienyl, methyl- or dimethyl- or pentamethylcyclopentadienyl and
trimethylsilylcyclopentadienyl .
~ CA 0220~117 1996-0~-12 ~
-
- 15-
The primary amines can correspond to the formula R26NH2, the secondary amines can
correspond to the formula R26R27NH and the tertiary amines can correspond to the formula
R26R27R28N, in which R26 is C1-C,8alkyl, C5- or C6cycloalkyl which is unsubstituted or
substituted by C,-C4alkyl or C,-C4alkoxy, or C6-C,8aryl or C7-C,2aralkyl which are
unsubstituted or substituted by C1-C4alkyl or C1-C4alkoxy, R2, independently has the meaning
of R26, or R26 and R27 LogeLl,er are tetramethylene, pentamethylene, 3-oxa-1,5-pentylene or -
CH2-CH2-NH-CH2-CH2- or-CH2-CH2-N(C,-C4alkyl)-CH2-CH2-, and R28 independently has the
meaning of R26. The alkyl preferably contains 1 to 12, and particularly p,t ferably 1 to 6 C
atoms. The aryl prer~rably contains 6 to 12 C atoms and the aralkyl preferably contains 7 to
9 C atoms. Exa,nples of amines are methyl-, dimethyl-, trimethyl-, ethyl-, diethyl-, triethyl-,
methyl-ethyl-, dimethyl-ethyl-, n-propyl-, di-n-propyl-, tri-n-butyl-, cyclohexyl-, phenyl- and
benzylamine, and py"olidi"e, N-methylpyrrolidine, p;"elidi"e, pi,uerd~i"e, morpholine and N-
methylmorpholine.
In a preferred subgroup, the non-photolabile ligands are H20, NH3 and C,-C4alkanols which
are unsubstitl ~ted or partly or completely fluorinated, or cyclopentadienyl. H20, NH3,
cyclopentadienyl, methanol and ethanol are especially preferred.
Sterically exacting substituents in the context of the invention are understood as meaning
those which shield the ruthenium and osmium atoms sterically. It has thus been found,
surprisingly, that linear alkyl groups as substituents in the phosphine ligands give ruthenium
compounds without any thermal activity for melall ,esis polymerization of strained
cycloolefins. It has also been found that in the case of osmium compounds, linear alkyl
groups as s~hstituents in the phosphine ligands su"~ lyly have an excellent
thermocatalytic activity for the metathesis polymeri~dlion of strained cycloolefins; ho/~evcr,
phosphine ligands with sterically exacting sl Ihstit~ ~ents are also preferably used for the
osmium compounds. It has furthermore been found that the steric shielding of
triphenylphosphi"e ligands is inadequ~te in ruthenium dihalides and ruthenium hydride-
halides, and such catalyts have only a moderate catalytic activity for the metathesis
polymerization of strained cyGloclerins. Sul,~ri~inyly, the catalytic activity can be increased
considerably if the tertiary phosphine groups contain phenyl which is suhstituted by alkyl or
alkoxy groups.
The phosphine ligands preferably correspond to the formulae Vl or Vla
CA 0220~ll7 l996-0~-l2
- 16-
PR29R3oR31 (Vl)
R2gR30P-Z1-PR29R3o (Vla)
in which
R29, R30 and R3, independently of one another are cx-branched C3-C20alkyl; C4-C,2cycloalkyl
which is unsl Ihstituted or sl Ihstituted by C,-C,8alkyl, C,-C,8haloalkyl or C,-C,8alkoxy; or
C6-C,6aryl which is unsuhstitl Ited or sl ~hstituted by C,-C,8alkyl, C~-C~8haloalkyl or
C,-C,8alkoxy;
the radicals R28 and R30 togelher are tetra- or penlar"ell,ylene which is unsubstituted or
sl ~hstituted by
C,-C6alkyl, C,-C6haloalkyl or C,-C6alkoxy, or tetra- or pentamethylene which is unsl Ihstituted
or substituted by C,-C6alkyl, C,-C6haloalkyl or C,-C6alkoxy and fused with 1 or 2 1,2-
phenylene, and
R3, has the abovementioned meaning; and
Z, is linear or branched C2-C,2alkylene which is unsubstituted or sl ~hstituted by C,-C4alkoxy,
1,2- or 1,3-cycloalkylene which has 4 to 8 C atoms and is unsubstituted or substituted by
C,-C4alkyl or C1-C4alkoxy, or 1,2 or 1,3-heterocycloalkylene which has 5 or 6 ring members
and one heteroatom from the group consisting of O and N and is unsuhstituted or suhstituted
by C,-C4alkyl or C,-C4alkoxy.
The radicals R29, R30 and R3, are preferably identical rad;cals. Substituents are preferably in
one or both ortho- and/or meta-positions relative to the C atom of the P-C bond in the
phosphine.
Alkyl R29, R30 and R3, can contain 3 to 12, preferably 3 to 8, and particularly preferably 3 to 6
C atoms. It is preferably ol-branched alkyl, for example of the formula -CRbRCRd~ in which Rb
is H or C,-C,2alkyl, Rc is C,-C,2alkyl, and R~, is C,-C,2alkyl or phenyl which is unsl Ihstituted or
sl IhstihlPd by C,-C4alkyl or C,-C4alkoxy, and the sum of the C atoms in the radical -CRbRCRd
is 3 to 18. Examples of alkyl are i-propyl, i- and t-butyl, 1-methyl or 1,1-dimethylprop-1-yl, 1-
methyl- or 1,1-dimethylbut-1-yl, 1-methyl- or 1,1-dimethylpenty-1-yl, 1-methyl- or 1,1-
dimethylhex-1-yl, 1-methyl- or 1,1-dimethylhept-1-yl, 1-methyl- or 1,1-dimethyloct-1-yl, 1-
methyl- or 1,1-dimethylnon-1-yl, 1-methyl- or 1,1-dimethyldec-1-yl, 1-methyl- or 1,1-
dimethylundec-1-yl, 1-methyl- or 1,1-dimethyldodec-1-yl, 1-methyl- or 1,1-dimethyltridec-1-yl,
1-methyl- or 1,1-dimethyltetradec-1-yl, 1-methyl- or 1,1-dimethylpentadec-1-yl, 1-methyl- or
CA 0220~ll7 l996-0~-l2
- 17-
1,1-dimethylhexadec-1-yl, 1-methylheptadec-1-yl and phenyl-dimethyl-methyl. Preferred
examples are i-propyl and i- and t-butyl.
In the osmium compounds used, R29, R30 and R3, can also be linear alkyl having 1 to 18,
preferably 1 to 12, more preferably 1 to 8, and particularly preferably 1 to 6 C atoms, for
example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl and n-octyl.
Cycloalkyl R29, R30 and R3, is preferably C5-C8cycloalkyl, and particularly preferably Cs~ or
C6cycloalkyl. Some examples are cyclobutyl, cycloheptyl, cyclooctyl and, in particular,
cyclopentyl and cyclohexyl, which are prert:r~bly uns~ ~hstituted or substituted by 1 to 3 alkyl,
haloalkyl or alkoxy groups. Exa",ples of sllt-stituted cycloalkyl are methyl-, dimethyl-,
trimethyl-, methoxy-, dimethoxy-, trimethoxy-, trifluoromethyl-, bistrifluoromethyl and
tristrifluoromethylcyclopentyl and -cyclohexyl.
Aryl R29, R30 and R3, is preferably C6-C12aryl, and particularly prere:r~bly phenyl or naphthyl.
Examples of sl ~bstituted aryl are methyl-, dimethyl-, trimethyl-, methoxy-, dimethoxy-,
trimethoxy-, trifluoromethyl-, bistrifluorometl1yl and tristrifluoromethylphenyl.
Examples of optionally suhstituted or fused tetra- and pentamethylene bonded to the P atom
are
CH3 (~ ~
H7C / H3C H3C
Other suitable tertiary phosphines are cycloali~hdlics which have 6 to 8 ring carbon atoms
and are bridged with a =PRa group, for example
[~3 ' ~ ' ~) and ~3,
CA 0220~ll7 l996-0~-l2
- 18-
~ . .
in which Ra is C,-C6alkyl, cyclohexyl, or phenyl which is unsubstituted or sl~hstit~lted by 1 or
2 C,-C4alkyl.
In a preferred embodiment, the phosphine ligands cor,espond to the formula Vl, in which
R29, R30 and R31 independently of one another are ~-branched C3-C8alkyl, cyclopentyl or
cyclohexyl which are unsl Ihstitl Ited or s' Ihstit~ ~ted by C,-C4alkyl, or phenyl which is
unsubstituted or substituted by C,-C4alkyl, C1-C4alkyl lsic], C1-C4alkoxy or trifluoromethyl.
Particularly prerer, ~d examples of phosphine ligands of the formula Vl are (C6H5)3P,
(C5H~)3P, (C6H")3P, (i-C3H,)3P, (i-C4Hg)3P, (t-C4Hg)3P, ~C2H5CH(CH3)]3P, [C2H5CH(CH3)2]3P,
(2-methylphenyl)3P, (2,3-dimethylphenyl)3P, (2,4-dimethylphenyl)3P, (2,6-dimethylphenyl)3P,
(2-methyl~-i-propylphenyl)3P, (2-methyl-3-i-propylphenyl)3P, (2-methyl-~-i-propylphenyl)3P
(2-methyl-6-i-propylphenyl)3P, (2-methyl-3-t-butylphenyl)3P, (2-methyl4-t-butylphenyl)3P,
(2-methyl-5-i-butylphenyl)3P, (2,3-di-t-butylphenyl)3P, (2,4-di-t-butylphenyl)3P, (2,5-di-t-
butylphenyl)3P and (2,6-di-t-butylphenyl)3P.
Suitable anions of inorganic or organic acids are, for example, hydride (He), halide (for
example F~, Cle Bre and le), the anion of an oxygen acid and BF4e, PF6e, SbF6e or AsF6e. It
should be mentioned that the abovementioned cyclopentadienyl is a ligand and an anion.
Further sl l -'- 'e anions are C,-C,2-, preferably C,-C6-, and particularly preferably
C,-C4alcoholates, which, in particular, are branched, for example correspond to the formula
RXRyRzC~Oe~ in which Rx is H or C,-C,Oalkyl, Ry is C,-C,Oalkyl and Rz is C,-C,Oalkyl or phenyl,
and the sum of the C atoms of Rx~ Ry and Rz is 11. Examples are, in particular, i-propyloxy
and t-butyloxy.
Other sllit-~'e anions are C3-C,8-, p~t:fer~bly C5-C,4-, and particularly preferably
C5-C,2acetylides, which can correspond to the formula RW-C=Ce, in which Rw is C,-C,6alkyl,
preferably a-branched C3-C,2alkyl, or is phenyl or benzyl which are unsubstituted or
suhstituted by 1 to 3 C,-C4alkyl or C,-C4alkoxy. Some exar, F'es are i-propyl-, i- and t-butyl-,
phenyl-, benzyl-, 2-methyl-, 2,6-dimethyl-, 2-i-propyl-, 2-i-propyl-6-methyl-, 2-t-butyl-, 2,6-di-t-
butyl- and 2-methyl-6-t-butylphenylacetylide.
The anions of oxygen acids can be, for example, sulfate, phosphate, perchlorate,perbromate, periodate, antimonate, arsenate, nitrate, carbonate, the anion of a
CA 0220~ll7 l996-0~-l2
- 19-
C,-C8carboxylic acid, such as, for exar"F'e, formate, acetate, propionate, butyrate, benzoate,
phenylacetate or mono-, di- or trichloro-or -Fluoroacetate, sulfonates, such as, for example,
methylsulfonate, ethylsulfonate, propylsulfonate, butylsulfonate, trifluoromethylsulfonate
(triflate) or phenylsulfonate or benzylsulfonate which are optionally substituted by C,-C4alkyl,
C,-C4alkoxyl or halogen, in particular fluorine or bromine, for example tosylate, mesylate,
brosylate, p-methoxy- or p-ethoxyphenylsulfonate, pentafluorophenylsulfonate or 2,4,6-
triisopropylsulfonate, and phosphates, for example methylphosphonate, ethylphosphonate,
propylphosphonate, butyl,uhosphonate, phenylphosphonate, p-methylphosphonate or
benzylphosphonate.
He, Fe, Cle, Bre, BF4e, PF6e, SbF6e, AsF6e, CF3SO3e, C6H5-SO3e, 4-methyl-C6H5-SO3e,
3,5-dimethyl-C6H5-SO3e, 2,4,6-trimethyl-C6H5-SO3e and 4-CF3-C6H5-SO3e are particularly
preferred.
In a preferred embodiment, the ruthenium and osmium compounds particularly preferably
correspond to the formulae Vll, Vlla, Vllb, Vllc or Vlld
Me2 (L,)2(L2)(Y,e)2 (Vll)
Me2 (L,)3(y, )2 (Vlla)
Me2 (L,)2L3((Y,3) (Vllb)
Me2 (L,)3L4(Y,e)2 (Vllc)
Me2~3L,(L2)3(Y,e)2 (Vlld)
in which
Me is Ru or Os;
Y, is the anion of a monobasic acid;
L, is a phosphine of the formula Vl or Vla,
L2 iS a neutral ligand;
L3 iS a cyclopentadienyl which is unsllhstihlted or suhstituted by C,-C4alkyl; and
CA 0220~117 1996-0~-12
- 20 ~
r
L4 is CO.
The above preferences apply to the individual meanings of L" L2, L3 and Y,.
In a particularly preferred embodiment, L2 in formula Vll and Vlld is a C,-C4alkanol, Yl in the
formulae Vll, Vlla and Vlld is an anion of a monobasic acid, Y, in formula Vllb is Cl or Br, Y,
in formula Vllc is H, and L, in the formulae Vll to Vlld is tri-i-propylphosphine,
tricyclohexylphosphine, triphenylphosphi"e or triphenylphosphine which is suhstitllted by 1 to
3 C1-C4alkyl in the phenyl groups.
The ruthenium and osmium compounds to be used according to the invention are known or
can be prepar~d by known and analogous processes starting from the metal halides lfor
example MeX3, (Me-areneX2)2 or [Me(diolefin)X2]2] and reaction with phosphines and agents
which form ligands.
The composition according to the invention can addilionally comprise other non-volatile
open-chain comonomers which form copolymers with the strained cycloolefins. If dienes, for
example, are co-used, c,osslil.ked polymers can form. Some examples of such comonomers
are ol~.,"ically mono- or di-unsaturated compounds, such as olefins and dienes from the
group consisli"g of pentene, hexene, heptene, octene, decene and dodecylene, acrylic and
methacrylic acid, esters and amides thereof, vinyl ether, styrene, butadiene, isoprene and
chlorobutadiene .
The other olehns which are cap-'le of meldll,esis polymerization are contained in the
composition according to the invention, for example, in an amount of up to 80 % by weight,
preferably 0.1 to 80 % by weight, more preferably 0.5 to 60 % by weight, and particularly
preferably 5 to 40 % by weight, based on the total amount of compounds of the formula I
and other olefins c~p-'-le of meLdll,esis polymerization.
The composition accordi"g to the invention can comprise formulation auxiliaries. Known
auxiliaries are a"li~ldlics, antioxidants, light sl~hi';~er~, plasticizers, dyes, pigments, fillers,
reinforcing fillers, lubricants, adhesion promoters, viscosity-increasing agents and mold
release auxiliaries. The fillers can be present in surprisingly high proportions without
adversely influencing the polymeri,dlion, for example in amounts of up to 70 % by weight,
preferably 1 to 70 % by weight, more preferably 5 to 60 % by weight, particularly preferably
10 to 50 % by weight, and espe-,ia"y preferably 10 to 40 % by weight, based on the
CA 0220~ll7 l996-0~-l2
-21 -
composition. A very large number of fillers and reinforcing fillers for improving the optical,
physical, mechanical and electrical properties have been disclosed. Some examples are
glass and quartz in the form of powders, beads and fibers, metal and semimetal oxides,
carbonates, such as MgCO3, CaCO3 and dolomite, metal sulfates, such as gypsum and
baryte, naturally occurring and synthetic silicates, such as talc, zeolites, wollastonite and
felspars, aluminas, such as china clay, rock powders, whiskers, carbon fibers, synthetic
fibers, powdered plastics and carbon black. Viscosity-increasing agents are, in particular
metathesis polymers which contain ol~ri, lically unsaturated groups and can be incorporated
into the polymer during the polymerization. Such metathesis polymers are known and are
commercially obtainable, for example under the tradename Vestenamere~. Other viscosity-
increasing agents are polybut~iene, polyisoprene or polychlorobutadiene, as well as
copolymers of butadiene, isoprene and chloroprene with olefins. The viscosity increasing
agents can be contained in an amount of 0.1 to 50, preferably 1 to 30, and particularly
preferably 1 to 20 % by weight, based on lthe composilion.
Catalytic quanliLies in the context of the present invention preferably means an amount of
0.0001 to 20 mol%, particularly preferably 0.001 to 15 mol%, and especially pr~rerdbly 0.001
to 10 mol%, based on the amount of the monomer.
The invention also relates to a process for thermal metdll ,esis polymerization, which is
chara~;leri~ed in that a composition of (a) at least one strained cycloolefin and (b) a catalytic
quantity of at least one divalent-cationic compound of ruthenium or osmium in which the
ruthenium or osmium compound contdi"s a metal atom to which are bound 1 to 3 tertiary
phosphine ligands with, in the case of ruthenium compounds, sterically exacting
substituents, optionally non-photolabile neutral ligands and anions for charge balancing, with
the proviso that in ruthenium (trisphen~,lpl-osphi"e).lil, ' ~'es or hydride-halides the phenyl
groups are substihlted by C,-C,8alkyl, C,-C,8haloalkyl or C,-C,8alkoxy, is polymerized.
The process accorcli"g to the invention can be carried out in the presence of an inert solvent.
A particular advantage of the process according to the invention is one that, in the case of
liquid monomers, the process can be carried out without the use of a solvent. Inert means
that the choice of solvent depends on the reactivity of the ruthenium and osmiumcompounds, for example that protic polar solvents are not used if suhstitution reactions, such
as the replacement of halogen by alkoxy, are to be expected.
CA 0220~117 1996-0~-12
- 22 -
Suitable inert solvents are, for example, protic-polar and aprotic solvents, which can be used
by themselves or in mixtures of at least two solvents. Examples are: ethers (dibutyl ether,
tetrahydrofuran, dioxane, ethylene glycol monomethyl or dimethyl ether, ethylene glycol
monoethyl or diethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether),
halogenated hydrocarbons (methylene chloride, chloroform, 1,2-dichloroethane,
1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane), carboxylic acid esters and lactones (ethyl
acetate, methyl propionate, ethyl benzoate, 2-methoxyethyl acetate, ~-butyrolactone,
~-valerolactone, piv '~lactone), carboxylic acid amides and lactams
(N,N-dimethylformamide, N,N-diethylfor-"ar"ide, N,N-dimethylacetamide, tetramethylurea,
hexamethylphosphoric acid triamine, ~-butyrolactam, ~-caprolactam, N-methylpyrrolidone, N-
acetylpyrrolidone, N-methylcaprolactam), sulfoxides (dimethyl sulfoxide), sulfones (dimethyl
sulfone, diethyl sulfone, trimethylene sulfone, tel,~n,~ll,ylene sulfone), tertiary amines (N-
methylpiperidine, N-methylmorpholine), aliphatic and aromatic hydrocarbons, for example
petroleum ether, pentane, hexane, cyclohexane, methylcyclohexane, benzene or substituted
benzenes (chlorobenzene, o-dichlorobenzene, 1,2,4-trichlorobenzene, nitrobenzene,
toluene, xylene) and nitriles (acetonitrile, prop.onil,i!e, ben~onillile, phenylacetonillile).
Preferred solvents are protic polar and non polar solvents.
Preferred solvents are alkanols and aromatic hydrocarbons, and mixtures of such solvents.
A particular advantage of the catalysts to be used according to the invention is their stability
to water and polar protic solvents, which can therefore likewise be used as solvents.
It is to be particularly e"~phasi~ed that the composilions of an optionally suhstituted
cycloolefin and catalyst which are employed according to the invention in the process are
often insensitive to oxygen, which allows storage and a reaction procedure without an inert
gas. Many of these compositions also have a good storage stability, which likewise simplifies
their processing.
The monomers of the formula I and the catalysts employed for the process according to the
invention can be stored both separately and together as a mixture, since the catalyst used
has a particularly high stability. Before the photochemical polymerization, the mixture can be
stored as a ready-to-use formulation, which is of advantage for use of the process according
to the invention on a large industrial scale. Storage and processing do not have to be carried
out with exclusion of light, since the catalysts used are not capa~'e of initiating
photometathesis polymerization.
CA 0220~ll7 l996-0~-l2
The reaction temperature essentially depends on the activity, the amount and the heat
stability of the catalysts used. Some catalysts are so active that they are capable of already
initiating the polymerization at room temperature.
The process according to the invention can be carried out at room temperature or slightly
elevated temperature, preferably at least 40C, and more preferably at least 60C. In
particular, the process according to the invention is carried out at temperatures from 40 to
300C, preferably 40 to 250C, particularly prer~rdbly 40 to to [sic] 200C, and especially
preferably 60 to 140C. After the polymerization, it may be advantageous to after-heat the
polymers at elevated temperatures, for example 80 to 200C.
As is known, the cycloolefins are strained rings. Cyclohexene generally cannot be
polymerized by olefin metathesis. This exception is known to the expert as described, for
example, in Ivin ~Ivin, K.J. in: Ivin, K.J., Saegusa, T. (editors), Ring-Opening Polymerisation
1:139-144 Elsevier Applied Science Publishers, London and New York (1984)].
The polymers prepared according to the invention can be homopolymers or copolymers with
random distribution of the structural units, graft polymers or block polymers, and crosslinked
polymers of this type. They can have an average molecular weight (Mw) of, for example,
500 up to 2 million daltons, preferably 1000 to 1 million daltons (determined by GPC by
comparison with polystyrene standards of narrow distribution). If the cycloolefins contain at
least 2 double bonds, crosslinked polymers can also be formed.
Thermoplastically deformable materials for the production of all types of shaped articles and
coatings can be prepared by the process according to the invention. Shaping and
polymerization are pr~ferdbly combined in solvent-free reactive systems, it being possible for
processing procedures such as injection molding, extrusion and polymerization inpredetermined forms (if appropriate under pressure) to be used.
The polymers according to the invention can have very different properties, depending on
the monomer used. Some of them are distinguished by a very high permeability to oxygen,
low dielectric constants, good heat stability and low absor~lion of water. Others have
outstanding optical properties, for example high transparency and low refractive indices. The
low shrinkage is furthermore to be emphasized in particular. They can therefore be used in
very different industrial fields.
~ CA 0220~117 1996-0~-12 ~
-
- 24 -
As layers on the surfaces of carrier materials, the compositions according to the invention
are distinguished by a high adhesive strength. The coated materials are furthermore
distinguished by a very high surface smoolllness and gloss. Of the good mechanical
properties, the low shrinkage and the high impact strength, as well as the heat stability is
[sic] to be emphasized in particular. The easy release from the mold and the high resistance
to solvents is [sic] furthermore to be mentioned.
These polymers are suit~hle for the production of medical equipment, i, l Iplanl~ or contact
lenses; for the production of electronic componenl:,; as binders for coatings; as photocurable
compositions for model construction or as adhesives for gluing suL,~LIdtes with low surface
energies (for example Teflon, polyethylene and polypropylene). The polymers prepared
according to the invention can also be used for the production of coali,)gs by
photopolymerization, it being possible on the one hand for clear (Llansparent) and even
pigmented compositions to be used. Both white and colored pigments can be used. The
production of shaped articles by thermoplastic shap.ng processes for all types of commodity
articles may furthermore be mentioned.
The polyll,er '-le compositions to be used according to the invention are also suitable for
the production of protective coatings. The invention also relates to a variant of the process
according to the invention for the production of coated materials in which a composition of a
cyclical olefin, catalyst and optionally solvent is applied as a layer to a carrier, for example by
dipping, brushing, pouring, rolling, knife-coating or whirler pouring processes, the solvent is
removed, if appropri~le, and the layer is heated for polymerization. Surfaces of SUL)SLI ~les
can be modified by this process.
The present invention also relates to a carrier material which is coated with an oligomer or
polymer according to the invention and comprises a closslinl~illg agent. The present
invention also relates to a carrier material which is coated with an oligomer or polymer
according to the invention. These materials are sllit~l-'e for the production of protective
coatings or images in relief by irradiation (if appropriate under a photo,l~ask) and suhsequent
development with a solvent. Suitable crosslinking agents, which can be conL~ined, for
example, in an amount of 0.01 to 20 % by weight, are, above all, organic bis~ides, in
particular the commercially available 2,6-bis(4-azidobenzylidene)-4-methyl-cyclohexanone.
The present invention furthermore also relates to a coated carrier material, which is
characterized in that a layer of (a) at least one strained cycloolefin and (b) a catalytic
CA 0220~117 1996-0~-12
.. --
- 25 -
quantity of at least one divalent-cationic compound of ruthenium or osmium, in which the
compound of ruthenium or osmium conlai. ,s a metal atom to which are bound 1 to 3 tertiary
phosphine ligands with, in the case of the ruthenium compounds, sterically exacting
substituents, optionally non-photolabile neutral ligands and anions for charge balancing, with
the proviso that in ruthenium (trisphenylphosphine) dihalides or hydride-halides the phenyl
groups are substituted by C,-C,8alkyl, C,-C,8haloalkyl or C,-C18alkoxy, is applied to a carrier.
The present invention also relates to the use of a divalent-cationic compound of ruthenium or
osmium, in which the compound of ruthenium or osmium conldi"s a metal atom to which are
bound 1 to 3 tertiary phosphine ligands with, in the case of the ruthenium compounds,
sterically exacting s~ ~bstituents, optionally non-pholo';~ neutral ligands and anions for
charge balancing, with the proviso that in ruthenium (trisphenyl,~,hosph;"e)dihalides or
hydride-halides, the phenyl groups are s~ ~hstituted by C,-C18alkyl, C,-C,8haloalkyl or
C,-C,8alkoxy, as catalysts for thermal metathesis polymerization of strained cycloolefins.
Suitable carrier rndLel '?~5 are, for example, those of glass, minerals, ceramics, plastics,
wood, semimetals, metals, metal oxides and metal nitrides. The layer thicknesses essentially
depend on the desired use and can be, for example, 0.1 to 1000 I~m, preferably 0.5 to
500 ,um, particularly preferably 1 to 100 I~m. The coated materials are distinguished by a
high adhesive strength and good thermal and mechanical properties.
The production of the coated materials accordi"9 to the invention can be carried out by
known methods, for example brushing, knife-coating, pouring processes, such as curtain
coating or whirler pouring.
In the case of coatings, particularly good results are often achieved if cycloolefins which
addiLionally contain 1 to three, and preferably one further double bond and which, in the
context of the invention, are polycyclical fused ring systems or ring systems linked directly or
via bridge groups are used for the polymerization.
The following exdri,F'es illustrate the invention further.
Examples 1 and 2: Polymerization of dicyclopentadiene in bulk
2 9 of biscyclopentadiene are mixed with 12 9 of catalyst and the mixture is poured into a
mold. Polymerization is then carried out for the times and at the temperatures stated in
Table 1 and after-curing is carried out for 2 hours at 1 50C.
CA 1)2205117 1996-05-12
- 26 -
The following catalysts are used (abbreviations: MeOH: methanol, Tos: tosylate, Cp:
cyclopentadienyl, Ph: phenyl, Cy: cyclohexyl):
A = Ru(PCy3)2(MeOH)2(Tos)2
B = RuC12(PCy3)2
C = Ru(H)2(CO)(PPh3)3
D = RuCpCl(PPh3)3
E = RuCI2[P(2-methyl-C6H4)3]3
Table 1
Example CatalYst Conversion in %Time, te",perdLure Polymer*
A 100 12 hours; 80C Tg = 122C
2 B 100 12 hours; 100C Tg = 118C
* crosslinked
ExamPles 3 to 7: Polymerization of norbomene
500 mg of norbornene are dissolved in 3 ml of ch'oroform and the solution is mixed with
3 mg of catalyst. Polymerization is then carried out for the times and at the temperatures
stated in Table 2. RT in Table 2 means room temperature. The conversion is determined
after prec;~,iLdlion with ethanol.
Table 2
ExamPle CatalYst Conversion in %Time, ter"Peralure MwMw/Mn3 A 97.5 10 minutes; RT 540 k 1.9
4 B 93 15 minutes; RT 300 k 2.0
C 25 2 hours; 50C crosslinked
6 D 30 10 hours; 50C 80 k 2.4
7 E 65 10 hours; 50C crosslinl;ed
